Pipe lining material, cured product of pipe lining material, and method for producing cured product of pipe lining material

Abstract

Disclosed is a pipe lining material which contains a resin composition and a composite material (E) that contains a fiber base material (e). The resin composition contains an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a photopolymerization initiator (C), and a dye (D). The dye (D) has a maximum absorption wavelength in the wavelength range of 450 nm to 1100 nm. The content of the dye (D) in the resin composition is 0.003 part by mass or more relative to a total of 100 parts by mass of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

Description

Pipe lining material, cured product of pipe lining material, and method for manufacturing the cured product of pipe lining material

[0001] The present invention relates to a pipe lining material, a cured product of the pipe lining material, and a method for producing the cured product of the pipe lining material.

[0002] In recent years, deterioration of existing underground pipes, such as water pipes, sewer pipes, and electric power pipes, has become increasingly serious, and various methods for repairing these pipes have been proposed. For example, Patent Document 1 discloses a method for repairing existing pipes using a photocuring method, which includes a curing step of adhering a tubular lining material to the inner wall surface of the existing underground pipe, supplying compressed air to the inside of the lining material, and irradiating the inner surface of the lining material with light using a mobile light irradiation device installed inside the lining material to cure the lining material. Patent Document 1 also describes that the lining material can be a material obtained by impregnating an impregnated base material made of fiber or the like with a photocurable resin composition, and that the photocurable resin composition can be a material obtained by dissolving a polymerizable resin, such as an unsaturated polyester resin or a vinyl ester resin, in a solvent, such as styrene.

[0003] Compared with the heat curing method, the light curing method has a faster curing rate of the resin composition and a shorter construction time, and therefore the construction distance using the light curing method in repair work on existing pipes has been increasing in recent years. Furthermore, the light curing method has advantages over the heat curing method in that the resin composition has less cure shrinkage, is less likely to have poor curing, generates less heat during curing, and emits less flammable gas during curing.

[0004] In the photocuring method, for example, a gallium lamp, a metal halide lamp, a mercury lamp, etc. are used as a light source. Patent Document 2 also proposes a pipe lining method in which a resin layer is irradiated with light using a photocuring device that uses a light-emitting diode (LED) that mainly emits ultraviolet light. LEDs generate little heat, are energy-saving, and have a long life, making them excellent light sources.

[0005] JP 2020-82408 A JP 2008-142996 A

[0006] However, in conventional pipe lining materials (lining materials for pipe repair), the resin composition contained in the pipe lining material may be poorly cured, or the cured product of the obtained pipe lining material may have poor physical properties. For this reason, in order to improve the poor curing of the resin composition contained in the pipe lining material, extensive research has been conducted on the resin composition.

[0007] The present invention has been made under these circumstances, and its object is to provide a pipe lining material that can provide a cured product of the pipe lining material having good physical properties. It is also an object of the present invention to provide a cured product of the pipe lining material having good physical properties and a method for producing the same.

[0008] The present invention is based on the discovery that by adding a dye to the resin composition contained in the composite material contained in the pipe lining material, a cured pipe lining material having good heat resistance and bending properties can be obtained.

[0009] The present invention provides the following means: [1] A pipe lining material containing a composite material (E) including a resin composition and a fiber substrate (e), wherein the resin composition contains an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a photopolymerization initiator (C), and a dye (D), wherein the dye (D) has a maximum absorption wavelength in a wavelength range of 400 to 1100 nm, and the content of the dye (D) in the resin composition is 0.003 parts by mass or more per 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B). [2] A pipe lining material wherein the absorption coefficient of the resin composition for light having the maximum absorption wavelength of the dye (D) is 0.1 to 10,000 cm －１The pipe lining material of [1], wherein the dye (D) is at least one selected from dyes and pigments. [3] The pipe lining material of [1] or [2], wherein the dye (D) is at least one selected from dyes and pigments. [4] The pipe lining material of any of [1] to [3], wherein the ethylenically unsaturated group-containing resin (A) is at least one selected from the group consisting of unsaturated polyester resins, vinyl ester resins, (meth)acrylic resins, and urethane (meth)acrylate resins. [5] The pipe lining material of claim 1 or 2, wherein the thickness of the composite material (E) is 1.0 to 30.0 mm. [6] A cured product of the pipe lining material of any of [1] to [5]. [7] A method for producing a cured product of the pipe lining material of [6], comprising irradiating the pipe lining material with light having an absorption wavelength range of the photopolymerization initiator (C) and light having an absorption wavelength range of the dye (D) to cure it. [8] A method for producing a cured product of the pipe lining material of [7], wherein the irradiated light has a peak wavelength in a wavelength range in which the ratio of the absorbance of the dye (D) to the absorbance at the maximum absorption wavelength in the absorption wavelength range of the dye (D) is 0.3 or more. [9] A method for producing a cured product of the pipe lining material of [7] or [8], wherein the irradiated light has a peak wavelength in a wavelength range in which the ratio of the absorbance of the dye (D) to the absorbance at the maximum absorption wavelength in the absorption wavelength range of the dye (D) is 0.3 or more in the wavelength range of 400 to 1100 nm.

[10] A method for producing a cured product of the pipe lining material of [7] to [9], wherein the irradiated light is light emitted from a light emitting diode, and the light emitting diode includes light (1) in the absorption wavelength range of the photopolymerization initiator (C) and light (2) in the absorption wavelength range of the dye (D).

[11] A resin composition for a pipe lining material, comprising: an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a photopolymerization initiator (C), and a dye (D), wherein the dye (D) has a maximum absorption wavelength in a wavelength range of 400 to 1100 nm, and the content of the dye (D) is 0.003 parts by mass or more per 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

[0010] According to the present invention, a pipe lining material is provided that can produce a cured product of the pipe lining material having good physical properties. It is also possible to provide a cured product of the pipe lining material having good physical properties and a method for producing the same. The pipe lining material of the present invention can be suitably applied to, for example, repair of existing pipes using a photocuring method.

[0011] The definitions and meanings of terms and notations used in this specification are shown below. A preferred numerical range can be any combination of preferred lower and upper limits. The maximum absorption wavelength is the wavelength at which absorbance is maximized, and is not limited to one point in the absorption spectrum, but may exist at two or more points. Among the maximum absorption wavelengths, the wavelength at which absorbance is maximized is called the maximum absorption wavelength. The peak wavelength is the wavelength at which emission intensity is maximized, and is not limited to one point in the emission spectrum, but may exist at two or more points. Among the peak wavelengths, the wavelength at which emission intensity is maximized is called the maximum emission wavelength. (Meth)acrylic acid is a general term for acrylic acid and methacrylic acid. Similarly, (meth)acrylate is a general term for acrylate and methacrylate, and (meth)acryloyl is a general term for acryloyl and methacryloyl. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) are standard polystyrene-equivalent molecular weights determined by gel permeation chromatography (GPC). Specifically, they are measured by the method described in the Examples below. The molecular weight distribution is a calculated value of Mw / Mn. The acid value of the unsaturated polyester resin is the amount of potassium hydroxide (KOH) [mg] required to neutralize 1 g of unsaturated polyester resin, measured by a method in accordance with JIS K6901:2008. Specifically, it is measured by the method described in the Examples below. The deflection temperature under load of the cured product of the pipe lining material can be measured by a method in accordance with JIS K7191-1:2015, specifically, it is measured by the method described in the Examples. The flexural strength and flexural modulus of the cured product of the pipe lining material can be measured by a method in accordance with JIS K7171:2016, specifically, it is measured by the method described in the Examples.

[0012] [Pipe Lining Material] A pipe lining material according to an embodiment of the present invention (hereinafter also referred to as this embodiment) is a pipe lining material containing a composite material (E) including a resin composition and a fiber substrate (e), wherein the resin composition contains an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a photopolymerization initiator (C), and a dye (D), wherein the dye (D) has a maximum absorption wavelength in the wavelength range of 400 to 1100 nm. The content of the dye (D) in the resin composition is 0.003 parts by mass or more per 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B). In this way, by adding the dye to the resin composition, a cured product having good heat resistance and bending properties can be obtained.

[0013] The lining material of this embodiment is tubular and is used for repairing existing pipes and the like (hereinafter also simply referred to as "pipe rehabilitation"). Pipe rehabilitation is generally performed by placing a pipe lining material along the inner circumference of the pipe's inner surface, crimping the pipe lining material to the inner surface, and then curing the resin composition contained in the composite material (E) contained in the pipe lining material by irradiating it with light such as ultraviolet light or visible light. In this specification, placing a pipe lining material along the inner circumference of the pipe's inner surface, crimping the pipe lining material to the inner surface, and then curing the resin composition contained in the composite material (E) contained in the pipe lining material by irradiating it with light such as ultraviolet light, visible light, or infrared light is also referred to as pipe rehabilitation.

[0014] From the viewpoint of ease of pipe rehabilitation work, the pipe lining material preferably includes an inner film and an outer film. Also, from the same viewpoint, it is more preferable that the pipe lining material contains an inner film as the innermost layer on the inner surface of the pipe to be rehabilitation, an outer film as the outermost layer on the outer surface, and the composite material (E) between the inner film and the outer film, or that the pipe lining material contains an outer film as the innermost layer on the inner surface, an inner film as the outermost layer on the outer surface, and the composite material (E) between the inner film and the outer film.

[0015] It is preferable that the pipe lining material has a diameter that is approximately the same as the inner diameter of the pipe to be rehabilitated. This improves the strength of the pipe after rehabilitation. The inner diameter of the pipe lining material is not particularly limited, but is preferably 100 to 1500 mm, more preferably 130 to 1200 mm, and even more preferably 150 to 1000 mm. If the inner diameter of the pipe lining material is 100 mm or more, application during hardening is easy, and if the inner diameter of the pipe lining material is 1500 mm or less, workability during pipe rehabilitation work is good.

[0016] [Resin Composition] The resin composition of this embodiment includes an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a photopolymerization initiator (C), and a dye (D), and the content of the dye (D) is 0.003 parts by mass or more per 100 parts by mass of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B) combined. The resin composition of this embodiment is suitable for use as a pipe lining material. From the viewpoint of good physical properties of the cured product of the pipe lining material (hereinafter also simply referred to as the "cured product"), the total content of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 90% by mass or more but less than 100% by mass, more preferably 92.0 to 99.9% by mass, and even more preferably 95.0 to 99.9% by mass.

[0017] (Ethylenically unsaturated group-containing resin (A)) The ethylenically unsaturated group-containing resin (A) is a resin having polymerizability due to an ethylenically unsaturated group. The ethylenically unsaturated group-containing resin (A) is not particularly limited, and examples thereof include unsaturated polyester resins, vinyl ester resins, (meth)acrylic resins, and urethane (meth)acrylate resins. The ethylenically unsaturated group-containing resin (A) may be used alone or in combination of two or more. Of these, unsaturated polyester resins and vinyl ester resins are preferred, as they are more likely to provide good cured product properties, and unsaturated polyester resins are more preferred.

[0018] From the viewpoint of good physical properties of the cured product, the content of the ethylenically unsaturated group-containing resin (A) in the resin composition is preferably 30.0 mass% or more, more preferably 40.0 mass% or more, even more preferably 50.0 mass% or more, relative to 100 mass% in total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B), and is preferably 80 mass% or less, more preferably 70.0 mass% or less, even more preferably 60.0 mass% or less.

[0019] <Unsaturated polyester resin> The unsaturated polyester resin is preferably a reaction product of a diol and a dibasic acid. The unsaturated polyester resin can be produced using a diol and a dibasic acid as reaction raw materials by applying a known synthesis method using a condensation reaction.

[0020] Diols, which are reaction raw materials for unsaturated polyester resins, are compounds having two hydroxyl groups per molecule. From the viewpoint of good physical properties of the cured product, for example, alkanediols, glycol ethers, etc. are preferably used. The diols may be used alone or in combination of two or more. Examples of alkanediols include ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethylenediol, propylene glycol ... Examples of glycol ethers include methyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-octanediol, 1,2-nonanediol, 1,4-cyclohexanediol, 1,8-octanediol, 1,9-nonanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-di(4-hydroxycyclohexyl)propane, and hydrogenated products of bisphenol A, bisphenol F, and bisphenol S. Examples of glycol ethers include diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol. Of these, from the viewpoints of availability, ease of handling of the resin composition, production costs, and the like, 2-methyl-1,3-propanediol, ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, and hydrogenated bisphenol A are preferred, 2-methyl-1,3-propanediol, propylene glycol, neopentyl glycol, and hydrogenated bisphenol A are more preferred, and propylene glycol and neopentyl glycol are even more preferred.

[0021] Dibasic Acids The dibasic acids used as reaction raw materials for the unsaturated polyester resin preferably include ethylenically unsaturated group-containing dibasic acids and ethylenically unsaturated group-free dibasic acids. The dibasic acids also include acid anhydrides.

[0022] The unsaturated polyester resin is obtained by forming an ester bond through a reaction between 1 mole of a hydroxyl group of a diol and 1 mole of a carboxyl group of a dibasic acid. Therefore, the total amount of the dibasic acid to be blended when producing the unsaturated polyester resin is preferably 80 to 120 parts by mole, more preferably 90 to 110 parts by mole, and even more preferably 95 to 105 parts by mole, per 100 parts by mole of the diol, and may be 100 parts by mole.

[0023] Of the dibasic acids, the ethylenically unsaturated group-containing dibasic acid is preferably used in an amount of 30 to 80 molar parts, more preferably 40 to 70 molar parts, and even more preferably 45 to 65 molar parts, relative to 100 molar parts of the diol, from the viewpoint of good physical properties of the cured product. Of the dibasic acids, the ethylenically unsaturated group-free dibasic acid is preferably used in an amount of 20 to 70 molar parts, more preferably 30 to 60 molar parts, and even more preferably 35 to 55 molar parts, relative to 100 molar parts of the diol, from the same viewpoint.

[0024] The ethylenically unsaturated group-containing dibasic acid is a compound having two carboxy groups (including acid anhydrides) and at least one ethylenically unsaturated group in one molecule. The ethylenically unsaturated group-containing dibasic acid may be used alone or in combination of two or more. Examples of the ethylenically unsaturated group-containing dibasic acid include maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and chloromaleic acid. Among these, maleic anhydride and fumaric acid are preferred, and maleic anhydride is preferably used, from the viewpoints of availability, ease of handling of the resin composition, and production costs.

[0025] From the viewpoint of good physical properties of the cured product, the content of the ethylenically unsaturated group-containing dibasic acid in the dibasic acid is preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, still more preferably 45 mol% or more, relative to 100 mol% of the dibasic acid, and is preferably 80 mol% or less, more preferably 75 mol% or less, even more preferably 70 mol% or less, and still more preferably 65 mol% or less.

[0026] The ethylenically unsaturated group-free dibasic acid is a compound having two carboxy groups (including acid anhydrides) in one molecule and not having an ethylenically unsaturated group. The ethylenically unsaturated group-free dibasic acid may be used alone or in combination of two or more. Examples of dibasic acids not containing an ethylenically unsaturated group include phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid (1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid), naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, chlorendic acid (HETT acid), tetrabromophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, succinic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, 4-methylphthalic acid, 5-methylisophthalic acid, 5-methylterephthalic acid, etc. Of these, isophthalic acid and terephthalic acid are preferred from the viewpoints of availability, ease of handling of the resin composition, production costs, etc.

[0027] From the viewpoint of good physical properties of the cured product, the content of the dibasic acid not containing an ethylenically unsaturated group in the dibasic acid is preferably 20 mol% or more, more preferably 25 mol% or more, even more preferably 30 mol% or more, still more preferably 35 mol% or more, relative to 100 mol% of the dibasic acid, and is preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 60 mol% or less, and still more preferably 55 mol% or less.

[0028] From the viewpoint of ease of handling and good curing properties of the resin composition, the unsaturated polyester resin preferably has an acid value of 3.0 to 25.0 KOHmg / g, more preferably 5.0 to 20.0 KOHmg / g, and even more preferably 8.0 to 15.0 KOHmg / g.

[0029] From the viewpoints of ease of handling of the resin composition and good physical properties of the cured product, the weight average molecular weight (Mw) of the unsaturated polyester resin is preferably 5,000 to 20,000, more preferably 7,000 to 17,000, and even more preferably 9,000 to 15,000. From the same viewpoint, the number average molecular weight (Mn) of the unsaturated polyester resin is preferably 1,000 to 7,000, more preferably 2,000 to 6,000, and even more preferably 3,000 to 5,000. From the same viewpoint, the molecular weight distribution (Mw / Mn) of the unsaturated polyester resin is preferably 1.00 to 15.00, more preferably 1.50 to 10.00, and even more preferably 2.00 to 5.00.

[0030] <Vinyl ester resin> The vinyl ester resin is preferably a reaction product of an epoxy compound and an unsaturated monobasic acid. The vinyl ester resin may be a reaction product of reaction raw materials including an epoxy compound and an unsaturated monobasic acid, and, if necessary, a bisphenol compound, an unsaturated polybasic acid, etc. The vinyl ester resin can be produced using a known synthesis method based on an addition reaction, using an epoxy compound and an unsaturated monobasic acid as reaction raw materials. The obtained vinyl ester resin is diluted with an ethylenically unsaturated group-containing monomer (B) as necessary. The vinyl ester resin may be used alone or in combination of two or more types.

[0031] <Epoxy Compound> The epoxy compound used as a reaction raw material for the vinyl ester resin is a compound having at least two, preferably two, epoxy groups per molecule. One type of epoxy compound may be used alone, or two or more types may be used in combination. Examples of the epoxy compound include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AF epoxy resins, tert-butylcatechol epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, anthracene epoxy resins, glycidyl ester epoxy resins, biphenyl epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol epoxy resins, and naphthylene ether epoxy resins. Of these, from the viewpoints of availability, ease of handling of the resin composition, production costs, etc., bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AF type epoxy resins are preferred, and bisphenol A type epoxy resins are preferably used.

[0032] The epoxy compound preferably has an epoxy equivalent of 170 to 1,000, more preferably 170 to 500, and even more preferably 170 to 300, from the viewpoints of ease of synthesis of the vinyl ester resin and good curability of the resin composition.

[0033] <Unsaturated Monobasic Acid> The unsaturated monobasic acid is preferably a monocarboxylic acid having an ethylenically unsaturated group. The unsaturated monobasic acid may be used alone or in combination of two or more. Examples of the unsaturated monobasic acid include (meth)acrylic acid, crotonic acid, cinnamic acid, etc. Among these, from the viewpoint of ease of synthesis of the vinyl ester resin and good curability of the resin composition, (meth)acrylic acid and crotonic acid are preferred, (meth)acrylic acid is more preferred, and from the viewpoint of chemical resistance, methacrylic acid is even more preferred.

[0034] When the vinyl ester resin is a reaction product of an epoxy compound and an unsaturated monobasic acid, it is obtained by forming an ester bond by reacting 1 mole of the epoxy group of the epoxy compound with 1 mole of the carboxy group of the unsaturated monobasic acid. The amount of unsaturated monobasic acid used in producing the vinyl ester resin is preferably 30 mole parts or more, more preferably 40 mole parts or more, and even more preferably 50 mole parts or more of the carboxy group of the unsaturated monobasic acid per 100 mole parts of the epoxy group of the epoxy compound, from the viewpoint of good curability of the resin composition. Furthermore, from the viewpoint of making the viscosity of the resin composition easy to handle, it is preferably 120 mole parts or less, more preferably 110 mole parts or less, and even more preferably 105 mole parts or less. The amount may be 100 mole parts per 100 mole parts of the epoxy group of the epoxy compound.

[0035] <Bisphenol Compound> The vinyl ester resin preferably contains a bisphenol compound as a reaction raw material. The bisphenol compound may be used alone or in combination of two or more. Examples of the bisphenol compound include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z. Among these, from the viewpoints of availability, production cost, and viscosity of the resin composition that is easy to handle, bisphenol A, bisphenol E, bisphenol F, and bisphenol S are preferred, and bisphenol A, bisphenol E, and bisphenol F are more preferred. From the viewpoints of corrosion resistance, versatility, and price, bisphenol A is even more preferred.

[0036] When a bisphenol compound is contained as a reaction raw material for the vinyl ester resin, the total amount of the unsaturated monobasic acid and the bisphenol compound to be blended in producing the vinyl ester resin is preferably 80 to 120 parts by mole, more preferably 90 to 110 parts by mole, and even more preferably 95 to 105 parts by mole, per 100 parts by mole of epoxy groups of the epoxy compound, and may be 100 parts by mole.

[0037] When a bisphenol compound is contained as a reaction raw material for a vinyl ester resin, the amount of the unsaturated monobasic acid and the bisphenol compound blended in producing the vinyl ester resin is preferably 80 to 120 parts by mole, more preferably 90 to 110 parts by mole, and even more preferably 95 to 105 parts by mole, per 100 parts by mole of epoxy groups of the epoxy compound, and may be 100 parts by mole.

[0038] When a bisphenol compound is contained as a reaction raw material for a vinyl ester resin, the amount of the bisphenol compound to be blended in producing the vinyl ester resin is preferably 10 to 70 parts by mole, more preferably 20 to 60 parts by mole, and even more preferably 25 to 50 parts by mole, per 100 parts by mole of epoxy groups of the epoxy compound, from the viewpoint of good physical properties of the cured product.

[0039] The vinyl ester resin may contain an unsaturated polybasic acid as a reaction raw material. The unsaturated polybasic acid is a compound having at least two carboxy groups (including acid anhydrides) and at least one unsaturated group per molecule. The unsaturated polybasic acid may be used alone or in combination of two or more. Examples of unsaturated polybasic acids include maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, itaconic acid, tetrahydrophthalic acid, and hexahydrophthalic acid. Among these, from the viewpoints of availability, ease of handling of the resin composition, and production costs, maleic anhydride, fumaric acid, succinic acid, glutaric acid, and adipic acid are preferred, with succinic acid, fumaric acid, and maleic anhydride being more preferred, and fumaric acid being even more preferred.

[0040] When an unsaturated polybasic acid is contained as a reaction raw material for the vinyl ester resin, the amount of the unsaturated polybasic acid to be blended in producing the vinyl ester resin is preferably 0.5 to 15 parts by mole, more preferably 1 to 10 parts by mole, and even more preferably 3 to 8 parts by mole, per 100 parts by mole of the epoxy groups of the epoxy compound, from the viewpoint of good physical properties of the cured product.

[0041] From the viewpoint of ease of handling and good curing properties of the resin composition, the vinyl ester resin preferably has an acid value of 3.0 to 50.0 KOHmg / g, more preferably 5.0 to 40.0 KOHmg / g, and even more preferably 10.0 to 35.0 KOHmg / g.

[0042] From the viewpoints of ease of handling of the resin composition and good physical properties of the cured product, the weight average molecular weight (Mw) of the vinyl ester resin is preferably 300 to 20,000, more preferably 500 to 10,000, and even more preferably 700 to 5,000. From the same viewpoint, the number average molecular weight (Mn) of the vinyl ester resin is preferably 200 to 15,000, more preferably 400 to 5,000, and even more preferably 600 to 3,000. From the same viewpoint, the molecular weight distribution (Mw / Mn) of the vinyl ester resin is preferably 1.00 to 5.00, more preferably 1.00 to 3.00, and even more preferably 1.10 to 2.50.

[0043] <Urethane (meth)acrylate resin> The urethane (meth)acrylate resin is preferably a polyurethane having a (meth)acryloyloxy group. The urethane (meth)acrylate resin can be produced by a known synthesis method. For example, an ethylenically unsaturated group-containing oligomer can be obtained by reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, and then reacting the unreacted isocyanato group with a hydroxyl group-containing (meth)acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound. The urethane (meth)acrylate resin may be used alone or in combination of two or more types.

[0044] (Ethylenically unsaturated group-containing monomer (B)) The ethylenically unsaturated group-containing monomer (B) is a monomer having polymerizability due to an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group (including an allyl group) and a (meth)acryloyl group. The ethylenically unsaturated group-containing monomer (B) may be used alone or in combination of two or more types.

[0045] Examples of the monomer having a vinyl group include styrene derivatives such as styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, tert-butylstyrene, vinylbenzyl butyl ether, vinylbenzyl hexyl ether, and divinylbenzyl ether; vinyl acetate, diallyl fumarate, diallyl phthalate, and triallyl isocyanurate.

[0046] Examples of monomers having a (meth)acryloyl group include (meth)acrylic acid, monofunctional (meth)acrylates, polyfunctional (meth)acrylates, acryloylmorpholine, 2-hydroxyethyl(meth)acrylamide, 2-hydroxyethyl-N-methyl(meth)acrylamide, and 3-hydroxypropyl(meth)acrylamide.

[0047] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, and ethylene glycol monohexyl ether. Examples of the acrylates include methyl ether (meth)acrylate, ethylene glycol mono-2-ethylhexyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, diethylene glycol monohexyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, and allyl (meth)acrylate.

[0048] Examples of polyfunctional (meth)acrylates include alkanediol di(meth)acrylates such as ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate; diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate. and polyoxyalkylene glycol di(meth)acrylates such as these, as well as trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol diacrylate monostearate, 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethoxylated bisphenol A di(meth)acrylate, and tris-(2-(meth)acryloxyethyl)isocyanurate.

[0049] Of these, from the viewpoints of availability, good physical properties of the cured product, production costs, and the like, styrene, methyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate are preferred as the ethylenically unsaturated group-containing monomer (B), and styrene and phenoxyethyl (meth)acrylate are preferably used.

[0050] From the viewpoint of good physical properties of the cured product, the content of the ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 20 to 70 mass%, more preferably 30 to 60 mass%, and even more preferably 40 to 50 mass%, relative to 100 mass% in total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

[0051] (Photopolymerization initiator (C)) The photopolymerization initiator (C) initiates the polymerization reaction of the resin composition. By irradiating a resin composition containing the photopolymerization initiator (C) with light in the absorption wavelength range of the photopolymerization initiator (C), the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B) are copolymerized to obtain a cured product. As the photopolymerization initiator (C), a polymerization initiator that generates radicals upon light irradiation is preferred, and from the viewpoint of reactivity, an intramolecular cleavage-type photopolymerization initiator that does not require a hydrogen donor is more preferred. The photopolymerization initiator (C) may be used alone or in combination of two or more types.

[0052] Examples of the photopolymerization initiator (C) include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-tert-butyldioxy-1-methylethyl)acetophenone; α-hydroxyalkylphenones such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenones such as benzophenone, 4-(1-tert-butyldioxy-1-methylethyl)benzophenone and 3,3',4,4'-tetrakis(tert-butyldioxycarbonyl)benzophenone; morpholines such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; acylphosphine oxides such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; and xanthones.

[0053] Among these, the photopolymerization initiator (C) is preferably one that absorbs ultraviolet light to generate radicals, and 2,2-dimethoxy-2-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and 1-hydroxycyclohexyl phenyl ketone are preferred. In a preferred embodiment of the present invention, two of them, 2,2-dimethoxy-2-phenylacetophenone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, are used in combination.

[0054] From the viewpoint of appropriately promoting curing of the resin composition, the total content of the photopolymerization initiator (C) in the resin composition is preferably 0.001 to 15.0 parts by mass, more preferably 0.01 to 5.0 parts by mass, and even more preferably 0.10 to 1.0 part by mass, relative to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

[0055] (Dye (D)) Dye (D) is a compound having a maximum absorption wavelength in the wavelength range of 400 to 1100 nm. It is presumed that when dye (D) having such light absorption properties is irradiated with light in the absorption wavelength range of dye (D), dye (D) absorbs the light, converting the light energy into thermal energy and increasing the temperature during curing, thereby improving curability and producing a cured product with good physical properties.

[0056] From the viewpoint of enabling the resin composition to obtain good curability by efficient use of irradiated light, it is preferable that the maximum absorption wavelength of the dye (D) is in the wavelength range of 400 to 1100 nm, i.e., the dye (D) preferably has a maximum absorption wavelength in the wavelength range of 400 to 1100 nm.

[0057] The wavelength range of the maximum absorption wavelength of the dye (D) is more preferably 460 nm or longer, even more preferably 480 nm or longer, still more preferably 500 nm or longer, and more preferably 1000 nm or shorter, even more preferably 900 nm or shorter, and still more preferably 850 nm or shorter.

[0058] From the same viewpoint, the absorption coefficient of the resin composition for light of the maximum absorption wavelength of the dye (D) is preferably 0.1 to 10,000 cm －１ , more preferably 0.5 to 1000 cm －１ , more preferably 1.0 to 500 cm －１ is.

[0059] The dye (D) may be a synthetic dye or a natural dye as long as it has the above-described light absorption characteristics. Furthermore, the dye (D) is preferably at least one selected from dyes and pigments, and is preferably capable of being uniformly mixed in the resin composition. Examples of the dye (D) include green, red, blue, and yellow dyes and pigments. The dye (D) may be used alone or in combination of two or more. Specific examples include anthraquinone-based, phthalocyanine-based, triphenylmethane-based, benzimidazolone-based, quinacridone-based, azochelate-based, azo-based, isoindoline-based, isoindolinone-based, pyranthrone-based, induthrone-based, anthrapyrimidine-based, dibromoanzanthrone-based, flavanthrone-based, perylene-based, perinone-based, quinophthalone-based, thioindigo-based, dioxazine-based, quinacridone-based, and xanthene-based dyes. Specific examples of the dye (D), from the viewpoint of good curability of the resin composition, include dyes such as the "Kayaset (registered trademark; hereinafter, omitted)" series "Red A-2G", "Red B", "Blue A-2R", "Blue N", and "Green A-G" (all manufactured by Nippon Kayaku Co., Ltd.), "Karenz (registered trademark; hereinafter, omitted) IRT" (manufactured by Resonac Corporation), and pigments such as "Chromofine (registered trademark; hereinafter, omitted) Red 6152EC" and "Cyanine Blue A-5109" (all manufactured by Dainichiseika Chemicals Co., Ltd.). Of these, "Kayaset Blue N" and "Karenz IRT" are preferred, and "Karenz IRT" is more preferred, due to their large absorption coefficient at the maximum absorption wavelength.

[0060] The content of the dye (D) in the resin composition is 0.003 parts by mass or more relative to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B) from the viewpoint of good curability of the resin composition and good physical properties of the cured product. When the content of the dye (D) in the resin composition is 0.003 parts by mass or more, the bending physical properties of the cured product become good. From the viewpoint of good physical properties of the cured product, the content of the dye (D) in the resin composition is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, even more preferably 0.02 parts by mass or more, and still more preferably 0.03 parts by mass or more, relative to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B), and is preferably 1.0 parts by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.2 parts by mass or less. That is, the content of the dye (D) in the resin composition is preferably 0.005 to 1.0 part by mass, more preferably 0.001 to 0.5 part by mass, even more preferably 0.02 to 0.2 part by mass, and even more preferably 0.03 to 0.2 part by mass, relative to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B). From the same viewpoint, the content of the dye (D) in the resin composition is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, and even more preferably 0.03% by mass or more, and is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less. That is, the content of the dye (D) in the resin composition is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.5 part by mass, even more preferably 0.02 to 0.2 part by mass, and still more preferably 0.03 to 0.2 part by mass. The content of the dye (D) in the resin composition can be adjusted appropriately depending on the shape and thickness of the cured product.

[0061] (Other Components) The resin composition may contain other components in addition to the ethylenically unsaturated group-containing resin (A), the ethylenically unsaturated group-containing monomer (B), the photopolymerization initiator (C), and the dye (D). The other components may be added within a range that does not impair the effects of the present invention. Examples of the other components include additives such as other resins, polymerization inhibitors, catalysts, thixotropes, curing accelerators, thickening aids, curing retarders, surfactants, interface modifiers, wetting and dispersing agents, antifoaming agents, leveling agents, coupling agents, light stabilizers, waxes, flame retardants, plasticizers, fillers, internal release agents, low-shrinkage agents, toners, viscosity reducers, anti-separation agents, and compatibilizers.

[0062] The polymerization inhibitor can be used to suppress the progress of the polymerization reaction of the resin composition. In this embodiment, the resin composition preferably contains a polymerization inhibitor. As the polymerization inhibitor, known ones can be used, and examples thereof include hydroquinone, methylhydroquinone, trimethylhydroquinone, phenothiazine, catechol, 4-tert-butylcatechol, copper naphthenate, etc. One type of polymerization inhibitor may be used alone, or two or more types may be used in combination.

[0063] The resin composition can be produced by mixing the ethylenically unsaturated group-containing resin (A), the ethylenically unsaturated group-containing monomer (B), the photopolymerization initiator (C), and the dye (D). The other components may be added and mixed as needed.

[0064] The order of mixing is not particularly limited. For example, the resin composition can be obtained by mixing and dissolving the ethylenically unsaturated group-containing resin (A) in the ethylenically unsaturated group-containing monomer (B), adding the photopolymerization initiator (C), the compound (D), and optionally other components, and mixing them. The mixing method is not particularly limited, and can be carried out using, for example, a disperser, a planetary mixer, a kneader, or the like. The kneading temperature is preferably 10 to 40°C, more preferably 15 to 30°C, and from the viewpoint of ease of mixing, etc., even more preferably 20 to 30°C.

[0065] [Composite Material (E)] The pipe lining material of this embodiment contains a composite material (E) including a resin composition and a fibrous base material (e). The composite material (E) is obtained by impregnating the fibrous base material (e) with the above-mentioned resin composition.

[0066] The shape of the composite material (E) may be a cylinder, a sheet, a tape, etc. From the viewpoint of obtaining a cured product with sufficient strength, the thickness of the composite material (E) is preferably 1.0 to 30.0 mm, more preferably 3.0 to 20.0 mm, and even more preferably 4.0 to 10.0 mm.

[0067] The content of the resin composition in the composite material (E) is preferably 20 to 95% by mass, more preferably 25 to 85% by mass, and even more preferably 25 to 75% by mass. If the content of the resin composition is 20% by mass or more, it is possible to impart appropriate flexibility to the pipe lining material, improving workability during pipe rehabilitation. If the content of the resin composition is 85% by mass or less, it is possible to impart sufficient strength to the cured product of the pipe lining material.

[0068] The content of the fiber base material (e) in the composite material (E) is preferably 5 to 80 mass%, more preferably 15 to 75 mass%, and even more preferably 25 to 75 mass%. When the content of the fiber base material (e) is 5 mass% or more, sufficient strength can be imparted to the cured product of the pipe lining material, and when the content of the fiber base material (e) is 80 mass% or less, appropriate flexibility can be imparted to the pipe lining material.

[0069] The total content of the resin composition and the fiber base material (e) in the composite material (E) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, from the viewpoint of imparting sufficient strength to the cured product of the pipe lining material, and may be 100% by mass.

[0070] (Fiber substrate (e)) From the viewpoint of mechanical strength, etc., examples of fibers constituting the fiber substrate (e) include synthetic fibers such as amide, nylon, aramid, vinylon, polyester, and phenolic resin; reinforcing fibers such as carbon fiber, glass fiber, metal fiber, and ceramic fiber; and composite fibers thereof. These may be used alone or in combination of two or more. Among these, aramid fiber, carbon fiber, and glass fiber are preferred, and glass fiber is more preferred from the viewpoint of strength, hardness, availability, price, etc. In particular, glass fiber and polyester fiber having optical transparency are preferred from the viewpoint of favorable curing of the resin composition contained in the composite material (E).

[0071] Examples of the form of the fiber substrate (e) include sheets, chopped strands, chopped fibers, milled fibers, etc. Examples of sheets include those formed by aligning multiple reinforcing fibers in one direction, bidirectional woven fabrics such as plain weave and twill weave, multiaxial woven fabrics, non-crimp woven fabrics, nonwoven fabrics, mats, knits, braids, and paper made from reinforcing fibers, etc. These may be used alone or in combination of two or more types, and may be a single layer or a multi-layer laminate. From the viewpoint of impregnation with the resin composition, the thickness of the sheet is, for example, preferably 0.01 to 5 mm in the case of a single layer, and in the case of a multi-layer laminate, the total thickness is preferably 1 to 20 mm, more preferably 1 to 15 mm.

[0072] [Inner Film] The inner film may be a resin film such as a polyethylene film, a polypropylene film, or a polyethylene terephthalate film. The inner film must be transparent to the light irradiated from the light irradiation device during pipe rehabilitation work. This allows the pipe lining material to be cured efficiently, allowing the pipe rehabilitation to be carried out appropriately. The inner film may be peeled off after the pipe lining material has cured.

[0073] The thickness of the inner film is not particularly limited, but is preferably 50 to 200 μm, more preferably 80 to 170 μm. If the thickness of the inner film is 50 μm or more, the inner film will not be damaged or wrinkled before or during pipe rehabilitation work, and sufficient strength can be imparted to the pipe. If the thickness of the inner film is 200 μm or less, the pipe lining material can be easily manufactured and the workability during pipe rehabilitation work is good.

[0074] [Outer Film] As with the inner film, a resin film can be used as the outer film. The outer film preferably has light-blocking properties. This can prevent external light from accelerating the hardening of the pipe lining material before the pipe rehabilitation work. Furthermore, during the pipe rehabilitation work, the irradiated light can be prevented from passing through the pipe lining material, allowing the pipe lining material to harden efficiently. As an outer film with light-blocking properties, for example, a laminated film having a colored coating layer, such as yellow, between two transparent polyethylene films can be used.

[0075] The thickness of the outer film is not particularly limited, but is preferably 5 to 100 μm, more preferably 10 to 90 μm. If the thickness of the outer film is 5 μm or more, the outer film will not be damaged or wrinkled before light irradiation during pipe rehabilitation work, and sufficient strength can be imparted to the pipe. If the thickness of the outer film is 100 μm or less, the production of the pipe lining material is easy, and workability during pipe rehabilitation work is good.

[0076] [Method for manufacturing pipe lining material] A conventionally known method can be used for manufacturing the pipe lining material. When manufacturing the pipe lining material of this embodiment, it is preferable to include the following steps 1 and 2, or the following steps 1 to 3.

[0077] [Step 1] Step 1 is a step of impregnating a fiber substrate (e) with a resin composition to obtain a composite material (E) containing the resin composition. In step 1, the resin composition may be impregnated into a fiber substrate (e) that is not laminated on its surface with an inner film or an outer film, or a fiber substrate (e) having at least one film selected from the group consisting of an inner film and an outer film laminated on its surface may be used. When a fiber substrate (e) having at least one film selected from the group consisting of an inner film and an outer film laminated on its surface is used, the resin composition is impregnated into the fiber substrate (e) via the inner film and the outer film.

[0078] The time for impregnating the fiber base material (e) with the resin composition is preferably 0.5 to 24 hours, more preferably 1 to 10 hours, and even more preferably 1.5 to 5 hours, from the viewpoint of reducing impregnation defects and uniformly impregnating the resin composition. The time from preparation of the resin composition, i.e., from production of the resin composition, to completion of impregnation with the resin composition is preferably 1 to 30 hours, more preferably 2 to 24 hours, and even more preferably 5 to 10 hours.

[0079] [Step 2] Step 2 is a step of laminating an inner film and an outer film onto a fiber substrate (e) or a composite material (E). The lamination method for the inner film and the outer film is not particularly limited, but examples include a method of applying a liquid film composition to the fiber substrate (e) or the composite material (E) and curing it to laminate, a method of laminating a film onto the fiber substrate (e) or the composite material (E) via an adhesive layer, and a method of directly laminating a film onto the fiber substrate (e) or the composite material (E). The inner film and the outer film may be laminated using different methods or the same method. The inner film and the outer film may be laminated independently before impregnating the fiber substrate (e) with the resin composition, or may be laminated onto the composite material (E) containing the resin composition. Furthermore, this step may be performed before or after step 3, which will be described later.

[0080] [Step 3] Step 3 is a step of processing into a cylindrical shape. Note that if a fiber base material (e) that is already cylindrical is used, step 3 does not need to be performed; it is performed when a sheet- or tape-shaped fiber base material (e) is used. Step 3 is a step performed after step 1, in which the composite material (E) is processed into a cylindrical shape by wrapping it around a mandrel having a diameter substantially the same as the diameter of the inner surface of the tube and fastening it with the resin composition contained in the composite material (E). Specifically, if the composite material (E) is in sheet form, after wrapping it around the mandrel, two longitudinal sides are overlapped by about 1 to 10 cm and fastened with the resin composition contained in the composite material (E). Also, if the composite material (E) is in tape form, the composite material (E) is spirally wound while overlapping by about 1 to 10 cm, and the overlapping portions are fastened with the resin composition contained in the composite material (E).

[0081] In step 3, if the composite material (E) containing the resin composition is wound around a mandrel with an inner film already placed on the mandrel, it is not necessary to laminate an inner film on the fiber base material (e) or the composite material (E) containing the resin composition, and this makes it easy to remove the mandrel after winding the composite material (E). Also, from the viewpoint of productivity, it is preferable to laminate an outer film after processing into a cylindrical shape.

[0082] The method for producing a pipe lining material may include a curing step in addition to the above steps 1 to 3. The curing step is a step for appropriately increasing the viscosity of the resin composition until it reaches a viscosity suitable for each step. It is preferably carried out after the resin composition has been impregnated into the fiber base material (e) or before the pipe rehabilitation work. The curing temperature in the curing step is preferably 10 to 40°C, more preferably 15 to 30°C, and even more preferably 20 to 30°C. The curing temperature can be adjusted as appropriate depending on the target viscosity of the resin composition, the curing time, etc.

[0083] From the viewpoint of quality stability, the storage period of the pipe lining material is preferably 1 to 6 months, more preferably 2 to 5 months.

[0084] [Cured product of pipe lining material] The cured product of the pipe lining material of this embodiment can be obtained by irradiating the pipe lining material of this embodiment with light such as ultraviolet light, visible light, infrared light, etc., to cure the resin composition contained in the composite material (E) contained in the pipe lining material. The cured product of the pipe lining material of this embodiment has good heat resistance and bending properties.

[0085] [Method for Producing Cured Pipe Lining Material] The method for producing the pipe lining material of this embodiment is carried out by irradiating the pipe lining material of this embodiment with light such as ultraviolet light, visible light, or infrared light.

[0086] Examples of light sources for the light irradiation device include metal halide lamps such as gallium lamps, mercury lamps, chemical lamps, xenon lamps, halogen lamps, mercury halogen lamps, carbon arc lamps, incandescent lamps, laser light, and light-emitting diodes (LEDs). From the viewpoint of work efficiency during pipe rehabilitation and efficient curing of the pipe lining material, metal halide lamps, gallium lamps, and LEDs are preferred, and LEDs are more preferred. Note that a light-emitting diode (LED) refers to an LED package, which is a light-emitting electronic component in which a light-emitting element is packaged.

[0087] The light irradiation device is not particularly limited as long as it has one or more irradiation units, but may have a lamp assembly configured by connecting a plurality of light irradiation lamps in series. The lamp assembly allows the pipe lining material to be cured efficiently.

[0088] From the viewpoint of good physical properties of the cured product, it is preferable to cure the pipe lining material of this embodiment by irradiating it with light having the absorption wavelength range of the photopolymerization initiator (C) and light having the absorption wavelength range of the dye (D). From the viewpoint of improving the curability of the resin composition and good physical properties of the cured product due to the temperature rise during curing caused by the conversion of light energy to thermal energy due to light absorption by the dye (D), the irradiated light preferably has a peak wavelength in a wavelength range including the maximum absorption wavelength of the dye (D). From the same viewpoint, it is preferable that the irradiated light has a peak wavelength in a wavelength range in which the ratio of the absorbance of the dye (D) to the absorbance of the maximum absorption wavelength in the absorption wavelength range of the dye (D) (hereinafter also referred to as relative absorbance) is 0.3 or more.

[0089] From the viewpoint of good physical properties of the cured product, it is preferable that the irradiated light is light emitted from a metal halide lamp, a gallium lamp, or an LED and contains light in the absorption wavelength region of the photopolymerization initiator (C) and light in the absorption wavelength region of the dye (D); and it is more preferable that the irradiated light is light emitted from a light-emitting diode (LED) and the LED contains light (1) in the absorption wavelength region of the photopolymerization initiator (C) and light (2) in the absorption wavelength region of the dye (D).

[0090] From the viewpoint of promoting the polymerization reaction of the resin composition by the photopolymerization initiator (C), the LED that emits light (1) preferably has a peak wavelength in the wavelength range of 250 to 400 nm. This wavelength range can be appropriately set corresponding to the maximum absorption wavelength of the photopolymerization initiator (C). In a preferred embodiment of the present invention, the maximum absorption wavelength of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide used as the photopolymerization initiator (C) is 366 nm, and an LED having a peak wavelength of 385 nm is used. The LED that emits light (1) may be composed of a single light-emitting element or may have multiple light-emitting elements, and may be mounted on an LED irradiator. The LED that emits light (1) may include a portion of light (1) in the absorption wavelength range of the photopolymerization initiator (C).

[0091] The LED that emits light (2) preferably exhibits maximum emission intensity in a wavelength range corresponding to the maximum absorption wavelength of dye (D), from the viewpoint of improving the curability of the resin composition and achieving good physical properties of the cured product due to the temperature rise during curing caused by the conversion of light energy to thermal energy due to light absorption by dye (D). From the same viewpoint, the LED that emits light (2) preferably has a peak wavelength in a wavelength range of 400 to 1100 nm where the ratio of the absorbance of dye (D) to the absorbance at the maximum absorption wavelength of dye (D) is 0.3 or more. The LED that emits light (2) may be composed of a single light-emitting element or may have multiple light-emitting elements, and may be mounted on an LED irradiator. The LED that emits light (2) may contain a portion of light (2) in the absorption wavelength range of dye (D). The LED may be packaged such that the light-emitting element that emits light (1) and the light-emitting element that emits light (2) are packaged in a single LED, or may be packaged in different LEDs.

[0092] When the light source of the light irradiation device is a metal halide lamp, the emission spectrum varies depending on the type and amount of metal halide in the lamp, so the optimum conditions vary depending on the type of metal halide lamp used, maximum power consumption, etc.

[0093] When the light source of the light irradiation device is a metal halide lamp, the irradiance of the light irradiated onto the pipe lining material is not particularly limited and is set appropriately depending on the shape and thickness of the pipe lining material, the equipment environment of the apparatus for producing the cured product, etc. However, from the viewpoint of improving the curability of the resin composition and obtaining good physical properties of the cured product, it is preferably 1.0 mW / cm ２ More preferably, 10.0 mW / cm ２ More preferably, 30.0 mW / cm ２ More preferably, 50.0 mW / cm ２ From the viewpoint of the heat resistance and energy efficiency of the light emitting device, it is preferably 1000 mW / cm ２ or less, more preferably 500 mW / cm ２ More preferably, 300 mW / cm or less ２ The following is the result.

[0094] When the light source of the light irradiation device is a metal halide lamp, the cumulative light amount of the light irradiated onto the pipe lining material is not particularly limited and is set appropriately depending on the shape and thickness of the pipe lining material, the equipment environment of the manufacturing device for the cured product, etc., but from the viewpoint of sufficient curing of the pipe lining material, it is preferably 0.1 J / cm ２ More preferably, 1.0 J / cm ２ More preferably, 5.0 J / cm ２ More preferably, 80 J / cm ２ or more, and preferably 5000 J / cm ２ or less, more preferably 2000 J / cm ２ More preferably, 1000 J / cm or less ２ More preferably, 300 J / cm or less ２ Below are the results.

[0095] When the light source of the light irradiation device is a metal halide lamp, the irradiation time of the light to the pipe lining material is appropriately set taking into consideration the integrated light amount and irradiance, and is preferably about 1 to 60 minutes, for example.

[0096] When the light source of the light irradiation device is a gallium lamp, the irradiance of the light irradiated onto the pipe lining material varies depending on the amount of gallium halide contained in the lamp, and the emission spectrum differs. In addition, the optimum irradiance conditions differ depending on the usage environment, etc., but from the viewpoint of sufficient hardening of the pipe lining material, it is preferably 1.0 mW / cm ２ More preferably, 10.0 mW / cm ２ More preferably, 20.0 mW / cm ２ More preferably, 50.0 mW / cm ２ From the viewpoint of the heat resistance and energy efficiency of the light emitting device, it is preferably 1000 mW / cm ２ or less, more preferably 500 mW / cm ２ More preferably, 200 mW / cm or less ２ More preferably, 100 mW / cm or less ２ The following is the result.

[0097] When the light source of the light irradiation device is a gallium lamp, the integrated light amount of the light irradiated onto the pipe lining material is not particularly limited and is set appropriately depending on the shape and thickness of the pipe lining material, the equipment environment of the manufacturing device for the cured product, etc., but from the viewpoint of sufficient curing of the pipe lining material, it is preferably 0.1 J / cm ２ More preferably, 1.0 J / cm ２ More preferably, 5.0 J / cm ２ More preferably, 80.0 J / cm ２ or more, and preferably 5000 J / cm ２ or less, more preferably 2000 J / cm ２ More preferably, 700 J / cm or less ２ More preferably, 200 J / cm or less ２ The following is the result.

[0098] When the light source of the light irradiation device is a gallium lamp, the irradiation time of the light to the pipe lining material is appropriately set taking into consideration the integrated light amount and irradiance, and is preferably about 1 to 60 minutes, for example.

[0099] When the light source of the light irradiation device is an LED, the cured product properties of the resin composition can be improved even if the total integrated light amount of light (1) and light (2) irradiated from the LED to the resin composition is approximately the same as the integrated light amount when only light (1) is irradiated. When there are multiple LEDs emitting light (1) and light (2), these LEDs may be mounted on the same LED irradiator and may be configured to emit light simultaneously or switch between them. Furthermore, the LED emitting light (1) and the LED emitting light (2) may be mounted on different LED irradiators.

[0100] The irradiance of each of the light (1) and light (2) is not particularly limited and is set appropriately depending on the shape and thickness of the pipe lining material, the facility environment when curing the pipe lining material, etc. The irradiance of light (1) is preferably 1.0 mW / cm from the viewpoint of improving the curability of the resin composition and obtaining good physical properties of the cured product. ２ or more, more preferably 5.0 mW / cm ２ or more, and more preferably 20.0 mW / cm２ From the viewpoint of the heat resistance and energy efficiency of the LED irradiator, it is preferable that the ２ or less, more preferably 200 mW / cm ２ or less, and more preferably 100 mW / cm ２ The irradiance of the light (2) is preferably 1.0 mW / cm from the viewpoint of increasing the temperature during photocuring and obtaining good physical properties of the cured product. ２ or more, more preferably 5.0 mW / cm ２ or more, and more preferably 20.0 mW / cm ２ From the viewpoint of the heat resistance and energy efficiency of the LED irradiator, it is preferable that the ２ or less, more preferably 200 mW / cm ２ or less, and more preferably 100 mW / cm ２ The following is the result.

[0101] The irradiation time of the light (1) and the light (2) on the pipe lining material is set appropriately taking into consideration the integrated light amount and irradiance, and is preferably about 1 second to 60 minutes, more preferably 10 to 50 minutes, and even more preferably 20 to 40 minutes.

[0102] The cumulative amount of light irradiated onto the pipe lining material by the light (1) is preferably 0.01 J / cm from the viewpoint of sufficient curing of the resin composition. ２ More preferably, 0.1 J / cm ２ More preferably, 1.0 J / cm ２ or more, and preferably 2000 J / cm ２ or less, more preferably 1000 J / cm ２ More preferably, 500 J / cm or less ２ From the same viewpoint, the integrated light amount of the light (2) irradiated onto the pipe lining material is preferably 0.01 J / cm ２ More preferably, 0.1 J / cm ２ More preferably, 1.0 J / cm ２ or more, and preferably 2000 J / cm ２or less, more preferably 1000 J / cm ２ More preferably, 500 J / cm or less ２ From the same viewpoint, the total integrated light amount of the light irradiated onto the pipe lining material by the light (1) and the light (2) is preferably 0.02 J / cm ２ More preferably, 0.2 J / cm ２ More preferably, 2.0 J / cm ２ or more, and preferably 4000 J / cm ２ or less, more preferably 2000 J / cm ２ More preferably, 1000 J / cm or less ２ The following is the result.

[0103] The method of irradiating the pipe lining material with light (1) and light (2) using an LED is not particularly limited. Irradiation with light (1) and light (2) may be performed simultaneously, sequentially, or continuously, or irradiation with light (1) and light (2) may be performed multiple times. From the viewpoint of efficiently producing a cured product by shortening the curing time, it is preferable to perform irradiation with light (2) before irradiation with light (1), or to perform irradiation with light (1) and irradiation with light (2) simultaneously, and it is more preferable to perform irradiation with light (1) and irradiation with light (2) simultaneously.

[0104] It is also preferable that the entire pipe lining material be irradiated with light as evenly as possible. From the viewpoint of efficiently producing a cured product by shortening the curing time, it is preferable to simultaneously irradiate with light from a plurality of metal halide lamps, gallium lamps, LEDs, etc., and it is more preferable to irradiate with light from an LED.

[0105] The present invention will be specifically described below based on examples, but the present invention is not limited to the following examples.

[0106] [Synthesis of Ethylenically Unsaturated Group-Containing Resin (A)] Unsaturated polyester resins (a1) and (a2) and vinyl ester resins (b1) and (b2) were synthesized as the ethylenically unsaturated group-containing resin (A). The physical properties of the ethylenically unsaturated group-containing resin (A) were measured as follows. The measurement results are shown in Table 1.

[0107] [Acid Value] In accordance with JIS K6901:2008 "Partial Acid Value (Indicator Titration Method)," the acid value was determined by measuring the mass of potassium hydroxide required to neutralize the acid components in the measurement sample using a mixed indicator of bromothymol blue and phenol red with an "Autoburette UCB-2000" (manufactured by Hiranuma Sangyo Co., Ltd.) Note that for the vinyl ester resins (b1) and (b2), the measurement sample was a mixture with the reactive diluent (ethylenically unsaturated group-containing monomer (B)) obtained in each Synthesis Example.

[0108] [Weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn)] The weight-average molecular weight Mw and number-average molecular weight Mn of the unsaturated polyester resin were measured by gel permeation chromatography (GPC) under the following conditions and calculated as standard polystyrene equivalent molecular weights. The molecular weight distribution Mw / Mn was calculated from the values ​​of the number-average molecular weight Mn and the weight-average molecular weight Mw.

[0109] <Measurement conditions> Apparatus: High-performance liquid chromatograph "Prominence (registered trademark)" (manufactured by Shimadzu Corporation) Column: "Shodex (registered trademark) LF-804" (manufactured by Resonac Corporation) Detector: Differential refractometer "Shodex (registered trademark) RI-71S" (manufactured by Resonac Corporation) Column temperature: 40°C Sample: 0.2% by mass solution of unsaturated polyester resin in tetrahydrofuran Developing solvent: tetrahydrofuran Flow rate: 1.0 mL / min

[0110] Synthesis Example 1 A 3 L four-neck separable flask equipped with a thermometer, a stirrer, a gas inlet tube, and a reflux condenser was charged with 224.6 g of propylene glycol (27.5 parts by mole relative to 100 parts by mole of total diols) as diols, 810.5 g of neopentyl glycol (2,2-dimethyl-1,3-propanediol) (72.5 parts by mole relative to 100 parts by mole of total diols), 472.6 g of isophthalic acid (26.5 parts by mole relative to 100 parts by mole of diols), 356.6 g of terephthalic acid (20.0 parts by mole relative to 100 parts by mole of diols), and 563.1 g of maleic anhydride (53.5 parts by mole relative to 100 parts by mole of diols), and the mixture was subjected to a condensation reaction at 215° C. for 10 hours under a nitrogen gas atmosphere to obtain an unsaturated polyester resin (a1).

[0111] Synthesis Example 2 An unsaturated polyester resin (a2) was obtained in the same manner as in Synthesis Example 1, except that the raw material composition shown in Table 1 was used.

[0112] Synthesis Example 3: 1512 g of "Epomic (registered trademark; hereinafter omitted) R140P" (bisphenol A-type epoxy resin; manufactured by Mitsui Chemicals, Inc., epoxy equivalent: 188) as an epoxy compound and 429 g of bisphenol A (47 moles per 100 moles of epoxy groups in the epoxy compound) were placed in a 5 L four-neck separable flask equipped with a thermometer, a stirrer, a gas inlet tube, and a reflux condenser. The mixture was stirred and mixed and heated to 80°C. Next, 3.9 g of triethylamine (manufactured by Daicel Corporation) was added as a catalyst, and the mixture was heated to 145°C and reacted for 1 hour under a nitrogen gas atmosphere. The epoxy equivalent of the epoxy compound was measured in accordance with JIS K7236:2001. The reaction product was cooled to 110°C, and 429 g (10% by mass based on the total amount of the components) of styrene, which was an ethylenically unsaturated group-containing monomer (B), was added as a reactive diluent. Furthermore, 0.04 g of copper naphthenate (0.0019 parts by mass per 100 parts by mass of the epoxy compound, bisphenol compound, and unsaturated monobasic acid) and 1.3 g of trimethylhydroquinone (0.056 parts by mass per 100 parts by mass of the epoxy compound, bisphenol compound, and unsaturated monobasic acid) were used as polymerization inhibitors, and 6.9 g of 2,4,6-tris(dimethylaminomethyl)phenol ("Seikuol (registered trademark) TDMP," manufactured by Seiko Chemical Co., Ltd., purity over 95% by mass) was used as an esterification catalyst (0.3 parts by mass per 100 parts by mass of the epoxy compound, bisphenol compound, and unsaturated monobasic acid) was added, and the mixture was heated to 110°C. Then, 365 g of methacrylic acid (53 moles per 100 moles of the epoxy group total of the epoxy compound) was added dropwise over 30 minutes, followed by heating to 130°C and reacting for 2 hours to produce vinyl ester resin (b1). The reaction product was cooled to 90°C, and 0.13 g (0.003 mass% based on the total amount of the blended components) of hydroquinone as a polymerization inhibitor was added, and 1,546 g (36 mass% based on the total amount of the blended components) of styrene, which is the ethylenically unsaturated group-containing monomer (B), was added as a reactive diluent, to obtain a mixture of vinyl ester resin (b1) and styrene (mass ratio 54.0 / 46.0).

[0113] Synthesis Example 4 In a 5 L four-neck separable flask equipped with a thermometer, a stirrer, a gas inlet tube, and a reflux condenser, 1950 g of Epomic R140P as an epoxy compound was heated to 80° C., and 407 g (10 mass % based on the total mass of the components) of phenoxyethyl methacrylate, which is the ethylenically unsaturated group-containing monomer (B), as a reactive diluent, 0.04 g of 5% copper naphthenate (0.0014 parts by mass relative to 100 parts by mass of the epoxy compound and the unsaturated monobasic acid), 0.9 g of methylhydroquinone (0.03 parts by mass relative to 100 parts by mass of the epoxy compound and the unsaturated monobasic acid), and 1.6 g of trimethylhydroquinone (0.057 parts by mass relative to 100 parts by mass of the epoxy compound and the unsaturated monobasic acid) as polymerization inhibitors, and 2,4,6-tris(dimethylaminomethyl)phenol ("Seikuol") as an esterification catalyst were added. 8.5 g (0.3 parts by mass per 100 parts by mass of the epoxy compound and unsaturated monobasic acid) of methacrylic acid was added and heated to 100°C. 891 g of methacrylic acid (100 moles per 100 moles of the epoxy group total of the epoxy compound) was added dropwise over 30 minutes, followed by a reaction for 2 hours to obtain vinyl ester resin (b2). The reaction product was cooled to 90°C, and 815 g (20% by mass based on the total amount of the components) of phenoxyethyl methacrylate, an ethylenically unsaturated group-containing monomer (B), was added as a reactive diluent to obtain a mixture of vinyl ester resin (b2) and phenoxyethyl methacrylate (mass ratio 70.0 / 30.0).

[0114]

[0115] [Production of Pipe Lining Material] Resin compositions were produced using each of the ethylenically unsaturated group-containing resins (A) obtained in the above synthesis examples, and then pipe lining materials were produced. Details of the dye (D) used in the production of the resin compositions are shown in Table 2. In accordance with JIS K 0115:2020, the absorption spectrum of a styrene solution containing 0.001% by mass of dye (D) was measured using an ultraviolet-visible spectrophotometer ("UV-1900i," manufactured by Shimadzu Corporation; a quartz cell for spectrophotometer "T-1-UV-10," manufactured by Tosoh Quartz Corporation). The relative absorbance in Table 2 is the ratio of absorbance to the absorbance at the maximum absorption wavelength in the wavelength range of 400 to 1100 nm.

[0116]

[0117] Example 1 (Production of Resin Composition) 100 parts by mass of a mixture (mass ratio 54.95 / 45.05) of unsaturated polyester resin (a1) dissolved in styrene, an ethylenically unsaturated group-containing monomer (B), was added with 0.11 parts by mass of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO) and 0.11 parts by mass of 2,2-dimethoxy-2-phenylacetophenone (DMPA) as photopolymerization initiators (C), and the mixture was stirred and mixed for 10 minutes at 2000 to 3000 rpm using a high-speed disperser ("Homodisper 2.5 Type," manufactured by Primix Corporation). 0.050 parts by mass of Karenz® IRT (manufactured by Resonac Corporation) was then added and stirred and mixed for 1 minute to produce a resin composition.

[0118] (Production of Pipe Lining Material) A pipe lining material was produced using the obtained resin composition as follows. A polyethylene film (manufactured by Ise Kasei Kogyo Co., Ltd.) having a length of 1400 mm and a thickness of 100 μm was wrapped around an aluminum plate having a width of 220 mm, a length of 1000 mm, and a thickness of 4 mm, with the end curved at R2, as an inner film, and the wrapped portion was heat-sealed using Vinylaid (manufactured by Hakko Corporation). Next, an 800 mm long glass fiber chopped strand mat (450 g / m) as a fiber substrate was placed on top of the inner film. ２A fiber substrate (design thickness 3.0 mm: 4 plies, glass content 40% by mass) containing the resin composition was wrapped around the fiber substrate, and simultaneously a defoaming roller was used to impregnate the fiber substrate with the resin composition. The amount of resin composition contained in the fiber substrate was 60% by mass. Furthermore, a polyethylene film 1400 mm long x 100 μm thick was covered on top of the fiber substrate containing the resin composition as an outer film, and the lapped portion was fixed with 50 mm wide masking tape (3M Japan Co., Ltd.). Next, the aluminum plate was pulled out and aged at 25°C for 2 days to obtain a pipe lining material.

[0119] (Production of Cured Resin Composition) A cured pipe lining material refers to a product in which the resin composition in the pipe lining material has cured, and the physical properties of the cured resin composition serve as an indicator of the physical properties of the cured pipe lining material. Therefore, a cured resin composition was produced, and the physical properties of the cured product were evaluated. A cured resin composition was produced using the obtained resin composition as follows. A mold was prepared using two glass plates (300 mm long x 300 mm wide x 5 mm thick) with a U-shaped NBR rubber spacer (10 mm wide, 4 mm thick) sandwiched along three sides of the plate surfaces and secured with clips. The resin composition was poured into the gap between the two glass plates of the prepared mold (inside the mold), and irradiated from one side of the glass plate surfaces using a metal halide lamp ("SHL-250", manufactured by Shonan Kosakusho Co., Ltd.). After 30 minutes of irradiation, the mold was left to stand at room temperature (23° C.) for 12 hours for curing, and then removed from the mold to obtain a cured resin composition.

[0120] The irradiance was adjusted by placing a separately prepared glass plate at the position where the mold was to be placed, and adjusting the position and output of the light-emitting device based on the irradiance value measured by directing the transmitted light of the irradiated light through the glass plate onto a light receiver of a spectroradiometer (USR-45VA, manufactured by Ushio Inc.).

[0121] [Examples 2 to 16, Comparative Examples 1 to 7] Cured resin compositions were produced in the same manner as in Example 1, except that the raw materials were blended in the compositions shown in Tables 3 to 8 and the resin compositions were cured using the light sources shown in Tables 3 to 8.

[0122] [Examples 17 to 30, Comparative Examples 8 to 16] (Production of resin compositions and production of pipe lining materials) Resin compositions and pipe lining materials were produced in the same manner as in Example 1, except that the raw materials were blended in the compositions shown in Tables 9 to 12.

[0123] (Production of cured resin composition) A mold was prepared using two glass plates (300 mm long x 300 mm wide x 5 mm thick) with a U-shaped NBR rubber spacer (10 mm wide, 4 mm thick) sandwiched along three sides of the plate surfaces and secured with clips. The resin composition was poured into the gap (inside the mold) between the two glass plates of the prepared mold, and LED light was irradiated onto the mold from the outside of the glass plate surfaces. The LED (LED (1)) emitting light (1) and the LED (LED (2)) each had the peak wavelengths shown in Tables 9 to 12. LED (1) and LED (2) were irradiated from opposite sides of the glass plates of the mold, and when irradiating both, they were irradiated simultaneously. After 30 minutes of irradiation, the mold was left to cure at room temperature (23°C) for 12 hours, and then removed from the mold to obtain a cured resin composition.

[0124] The irradiance was adjusted by placing a separately prepared glass plate at the position where the mold was to be placed, and adjusting the position and output of the LED irradiator based on the irradiance value measured by directing the transmitted light of the LED light through the glass plate onto the light receiver of a spectroradiometer (USR-45VA, manufactured by Ushio Inc.).

[0125] Examples 31 to 33 (Production of Resin Compositions) Resin compositions were produced in the same manner as in Example 1, except that the raw materials were blended in the compositions shown in Tables 13 and 14.

[0126] (Production of Pipe Lining Material) Using the obtained resin composition, a pipe lining material was produced as follows. A PET film (290 mm long x 290 mm wide x 125 μm thick) was laid on a glass plate (300 mm long x 300 mm wide x 5 mm thick), and a square-shaped NBR rubber spacer (10 mm wide x 4 mm thick) was placed along all four edges of the glass plate. A fiber substrate (e) shown in Tables 13 and 14, measuring 250 mm long x 250 mm wide, was placed inside the spacer, and the resin composition was impregnated using a defoaming roller. The above procedure was repeated so that there were seven layers of fiber substrate (e) in Example 31, eight layers of fiber substrate (e) in Example 32, and five layers of fiber substrate (e) in Example 33. After the operation was completed, a PET film (length 290 mm × width 290 mm × thickness 125 μm) was laid on the fiber substrate (e) impregnated with the resin composition, and a glass plate (length 300 mm × width 300 mm × thickness 5 mm) was placed on top of that, and then cured for 24 hours to obtain a pipe lining material.

[0127] (Production of Cured Pipe Lining Material) The obtained pipe lining material was irradiated from the outside of the glass plate surface using a metal halide lamp ("SHL-250", manufactured by Shonan Kosakusho Co., Ltd.) in Example 31, and LED light from one side in Examples 32 and 33. An LED emitting light (1) (LED (1)) and an LED emitting light (2) (LED (2) having the peak wavelengths shown in Table 14 were used. LED (1) and LED (2)) were irradiated simultaneously. The irradiance was adjusted by placing a separately prepared glass plate at the position where the mold was to be placed, and adjusting the position and output of the light-emitting device based on the irradiance value measured by directing the irradiated light transmitted through the glass plate to the light receiver of a spectroradiometer ("USR-45VA", manufactured by Ushio Inc.). After 30 minutes of irradiation, the material was left to stand at room temperature (23°C) for 12 hours to cure, and the glass plate and PET film were removed to obtain a cured pipe lining material.

[0128] The cured products of each resin composition produced in Examples 1 to 30 and Comparative Examples 1 to 16 were measured and evaluated for the following items (measurement environment: temperature 23°C, humidity 50% RH). The results of these measurements and evaluations are shown in Tables 3 to 12.

[0129] [Maximum Temperature During Photocuring (Photocurability)] The maximum temperature of the resin composition during photocuring was measured. The higher the maximum temperature, the better the photocurability.

[0130] [Head Deflection Temperature] Measurement was carried out under the following conditions in accordance with JIS K 7191-2:2015 Appendix A. <Measurement Conditions> - Apparatus: Head Deflection Temperature (HTD) Tester "S-3M" (manufactured by Toyo Seiki Co., Ltd.) - Test piece dimensions: Width 10 mm x Length 100 mm x Thickness 4 mm - Load: Bending stress 1.80 MPa - Specified deflection amount: 0.34 mm - Heating rate: 120°C / hr A cured product of the resin composition was cut to the above dimensions to prepare a test piece. The average of the measured values ​​for three test pieces was taken as the head deflection temperature of the cured product. If the head deflection temperature is 80.0°C or higher, it can be said that the cured product has good heat resistance.

[0131] [Flexural Strength and Flexural Modulus] Measurements were carried out in accordance with JIS K 7171:2016 under the following conditions. <Measurement Conditions> - Apparatus: "Autograph AGS-10kNX" (Shimadzu Corporation) - Analysis software: "TRAPEZIUM (registered trademark) LITE X" (Shimadzu Corporation) - Test piece dimensions: Width 10 mm x Length 80 mm x Thickness 4 mm - Test speed: 1.7 mm / min A cured product of the resin composition was cut to the above test piece dimensions to prepare a test piece. The average values ​​measured for five test pieces were used as the flexural strength and flexural modulus of each cured product. If the flexural strength is 100 MPa or more and the flexural modulus is 2800 MPa or more, the cured product can be said to have good flexural properties.

[0132] [Chemical Resistance] Measurements were carried out in accordance with JSWAS K-2 under the following conditions. 640.06 g of nitric acid 1.38 (special grade, manufactured by Kanto Chemical Co., Inc., 60% by mass nitric acid) was added to and mixed with 320.14 g of water to obtain a 40% by mass aqueous nitric acid solution. Subsequently, a cured resin composition processed into a 500 mm wide x 500 mm long x 4 mm thick sample was immersed in the 40% by mass aqueous nitric acid solution at 60°C for 5 hours in a 60°C environment, and the mass change rate before and after immersion was determined.

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143] The cured products of the pipe lining materials produced in Examples 31 to 33 were measured and evaluated for the following items (measurement environment: temperature 23°C, humidity 50% RH). The results of these measurements and evaluations are shown in Tables 13 and 14.

[0144] [Flexural Strength and Flexural Modulus] Measurements were carried out in accordance with JIS K 7171:2016 under the following conditions. <Measurement Conditions> - Apparatus: "Autograph AGS-10kNX" (Shimadzu Corporation) - Analysis software: "TRAPEZIUM (registered trademark) LITE X" (Shimadzu Corporation) - Test piece dimensions: Width 10 mm x Length 80 mm x Thickness 4 mm - Test speed: 1.7 mm / min The cured pipe lining material was cut to the above test piece dimensions to prepare a test piece. The average values ​​measured for five test pieces were taken as the flexural strength and flexural modulus of each cured product. If the flexural strength is 150 MPa or more and the flexural modulus is 5000 MPa or more, the cured product can be said to have good flexural properties.

[0145] [Barcol Hardness] A test specimen was obtained by processing the cured pipe lining material into a width of 100 mm, length of 100 mm, and thickness of 4 mm. Next, in accordance with JIS K7060:1995, a Barcol hardness tester ("GYZJ 934-1", manufactured by Barber-Coleman) was pressed against the backside of the light-irradiated surface of the test specimen, and the Barcol hardness of the test specimen was measured at 10 points on each of the front surface (light-irradiated surface) and back surface (surface opposite to the light-irradiated surface), and the average values ​​were taken as the Barcol hardness of the front and back surfaces of the cured pipe lining material. A Barcol hardness of 20 indicates that the cured pipe lining material has excellent hardness.

[0146]

[0147]

[0148] It has been confirmed that a cured pipe lining material having good heat resistance, bending properties, and chemical resistance can be obtained from the pipe lining material of the present embodiment, which contains a resin composition containing an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a photopolymerization initiator (C), and a dye (D), and a composite material (E) containing the resin composition and a fiber base material (e).

Claims

1. A pipe lining material containing a composite material (E) comprising a resin composition and a fibrous base material (e), The resin composition comprises an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a photopolymerization initiator (C), and a dye (D). Dye (D) has a maximum absorption wavelength in the wavelength range of 400 to 1100 nm. A pipe lining material wherein the content of the dye (D) in the resin composition is 0.003 parts by mass or more with respect to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

2. The absorption coefficient of the resin composition for light at the maximum absorption wavelength of the dye (D) is 0.1 to 10000 cm⁻¹. －１ The pipe lining material according to claim 1.

3. The pipe lining material according to claim 1 or 2, wherein the pigment (D) is at least one selected from dyes and pigments.

4. The pipe lining material according to claim 1 or 2, wherein the ethylenically unsaturated group-containing resin (A) is at least one selected from the group consisting of unsaturated polyester resin, vinyl ester resin, (meth)acrylic resin, and urethane (meth)acrylate resin.

5. The pipe lining material according to claim 1 or 2, wherein the thickness of the composite material (E) is 1.0 to 30.0 mm.

6. A cured product of the pipe lining material according to claim 1 or 2.

7. A method for producing a cured pipe lining material according to claim 6, wherein the pipe lining material is cured by irradiating it with irradiation light having light in the absorption wavelength range of the photopolymerization initiator (C) and light in the absorption wavelength range of the dye (D).

8. The method for producing a cured pipe lining material according to claim 7, wherein the irradiation light has a peak wavelength in a wavelength range where the ratio of the absorbance of the dye (D) to the absorbance at the maximum absorption wavelength in the absorption wavelength range of the dye (D) is 0.3 or more.

9. The method for producing a cured pipe lining material according to claim 8, wherein the irradiation light has a peak wavelength in the wavelength range of 400 to 1100 nm, where the ratio of the absorbance of the dye (D) to the absorbance at the maximum absorption wavelength of the dye (D) is 0.3 or more.

10. The method for producing a cured pipe lining material according to claim 8, wherein the irradiation light is light emitted from a light-emitting diode, and the light emitted from the light-emitting diode includes light (1) in the absorption wavelength range of the photopolymerization initiator (C) and light (2) in the absorption wavelength range of the dye (D).

11. The material comprises an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a photopolymerization initiator (C), and a dye (D). Dye (D) has a maximum absorption wavelength in the wavelength range of 400 to 1100 nm. A resin composition for pipe lining materials, wherein the content of the dye (D) is 0.003 parts by mass or more per 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).